EP1171406B1 - Procede de preparation de bi-aryles - Google Patents

Procede de preparation de bi-aryles Download PDF

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Publication number
EP1171406B1
EP1171406B1 EP00916828A EP00916828A EP1171406B1 EP 1171406 B1 EP1171406 B1 EP 1171406B1 EP 00916828 A EP00916828 A EP 00916828A EP 00916828 A EP00916828 A EP 00916828A EP 1171406 B1 EP1171406 B1 EP 1171406B1
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palladium
alkyl
group
formula
independently
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EP1171406A1 (fr
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Thomas Riermeier
Matthias Beller
Alexander Zapf
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

Definitions

  • the present invention relates to a method for producing biarylene with Catalysts based on palladium compounds with phosphite ligands
  • Biaryl compounds especially biphenyte compounds, have technical Importance as fine chemicals, intermediates for pharmaceuticals, optical Brighteners and agrochemicals.
  • a frequently used method for the synthesis of biarylene on a laboratory scale is the Suzuki reaction, in which iodine or bromoaromatics and, in exceptional cases, chloroaromatics are reacted with aryl, vinyl or alkylboronic acid derivatives in the presence of palladium catalysts.
  • Review articles describing this methodology can be found, for example, in N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457.
  • Catalysts used in the Suzuki reaction are generally palladium and nickel compounds. Despite the economic advantage of nickel catalysts (cf. AF Indolese, Tetrahedron Lett.
  • palladium catalysts are preferred over nickel catalysts because of the lower toxicity and the greater tolerance towards functional groups. If palladium catalysts are used, both palladium (II) and palladium (0) complexes are used in Suzuki reactions (cf. M. Beller, H. Fischer, WA Herrmann, K. ⁇ fele, C. Broßmer , Angew. Chem. 1995, 107 , 1992).
  • As catalytically active species coordinated unsaturated 14- and 16-electron palladium (0) species are formulated in the literature, which are stabilized with donor ligands such as phosphines. In particular when using cheaper educts such as aryl bromides or aryl chlorides, the addition of stabilizing ligands is required in order to achieve a satisfactory catalytic activation of the educts.
  • the object of the present invention is to provide a new method for the production of biarylene, which does not have the disadvantages of the known processes has, is suitable for large-scale implementation and biaryls in high Deliver yield, catalyst productivity and purity.
  • the carbon bridge E can have up to seven substituents which are selected independently of one another from the group of (C 1 -C 4 ) alkyl, O-alkyl- (C 1 -C 4 ), OH and Ar , where Ar has the same meaning as in formula (I).
  • Q 1 and Q 2 independently of one another are a (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 6 -C 10 ) - Aryl and / or (C 6 -C 10 ) aryloxy radical which are substituted by at least one halogen atom or a (C 1 -C 4 ) alkoxy or (C 1 -C 4 ) alkyl radical; or that Q 1 and Q 2 in the formula (IIIa) together represent an alkylenedioxy or alkylene group having one to four carbon atoms, which are optionally substituted by up to four (C 1 -C 4 ) alkyl and / or (C 6 -C 10 ) aryl radicals is substituted.
  • the radicals Ar and Ar ' can independently represent a heteroaromatic, with up to four further aromatic, heteroaromatic and / or aliphatic rings being fused onto the heteroaromatic ring.
  • the process according to the invention is particularly suitable for the synthesis of biarylene, in which Ar and Ar 'for a substituted phenyl, naphthyl, anthryl, phenanthryl, biphenyl radical and / or a five-, six- or seven-membered heteroaromatic compound with optionally nitrogen -, oxygen or sulfur atoms in the ring.
  • heteroaromatics such as substituted pyridines, pyrimidines, oxazoles, imidazoles, pyrazines, quinolines, indoles, furans, benzofurans and / or thiophenes are particularly preferred.
  • the process according to the invention has proven particularly useful for the preparation of compounds of the formula (I) in which the radicals Ar and Ar 'independently of one another have up to 5 substituents selected from the group consisting of alkyl- (C 1 -C 8 ), O -Alkyl- (C 1 -C 8 ), OCO-alkyl- (C 1 -C 8 ), N-alkyl 2 - (C 1 -C 8 ), phenyl, aryl, fluorine, chlorine, NO 2 , CN, COOH , CHO, SO 2 -alkyl- (C 1 -C 4 ), NH-alkyl- (C 1 -C 8 ), COO-alkyl- (C 1 -C 8 ), CONH 2 , CONH-alkyl- (C 1 -C 8 ), CO-alkyl- (C 1 -C 8 ), CO-phenyl and PO-phenyl 2 .
  • the reaction generally takes place in the presence of at least one solvent selected from the group consisting of water, aliphatic ethers, aromatic or aliphatic hydrocarbons, alcohols, esters, aromatic or aliphatic nitriles and dipolar aprotic solvents such as dialkyl sulfoxides, N, N-dialkylamides of aliphatic carboxylic acids or alkylated lactams.
  • at least one solvent selected from the group consisting of water, aliphatic ethers, aromatic or aliphatic hydrocarbons, alcohols, esters, aromatic or aliphatic nitriles and dipolar aprotic solvents such as dialkyl sulfoxides, N, N-dialkylamides of aliphatic carboxylic acids or alkylated lactams.
  • the solvent is preferably THF, dioxane, diethyl ether, diglyme, MTBE, DME, acetonitrile, toluene, xylenes, anisole, ethyl acetate, methanol, ethanol, butanol, ethylene glycol, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, N, N-dimethylacetamide, N, N- Dimethylformamide or N-methylpyrrolidone.
  • the base is preferably a carbonate, hydroxide or phosphate of lithium, Sodium, potassium, calcium, magnesium or cesium.
  • the base used can also have a positive effect on the course of the reaction by activating the arylboronic acid to form anionic boranate species.
  • activation can also be achieved by adding fluoride salts such as CaF 2 , NaF, KF, LiF, CsF or (C 1 -C 8 ) alkyl 4 NF.
  • the palladium catalysts of the general formula (IVa) or (IVb) used are generally generated in situ from at least one palladium (II) salt or a palladium (0) compound and the corresponding phosphite ligands.
  • the palladium (II) salt is preferably selected from the group of palladium (II) acetate, palladium (II) chloride, palladium (II) bromide, lithium tetrachloropalladate (II), palladium (II) acetylacetonate, palladium (II) propionate, palladium (II) chloride bis (acetonitrile), palladium (II) bis (triphenylphosphine) dichloride and palladium (II) chloride bis (benzonitrile).
  • the palladium (0) compound is particularly selected from the group of palladium (0) dibenzylidene acetone complexes, palladium (0) tetrakis (triphenylphosphite), palladium (0) tetrakis (triethylphosphite), palladium (0) tetrakis (triphenylphosphine) ), Palladium (0) -bis (tri-o-tolylphosphane), palladium (0) tricyclohexylphosphane-diallyl ether complex and palladium (0) bis (tricyclo-hexylphosphine).
  • a cocatalyst is selected from the group of halogen salts, in particular a halide of the alkali elements and / or alkaline earth elements, an ammonium halide and / or a phosphonium halide, preferably a bromide and / or chloride.
  • the halogen salts LiBr, LiCl, NaBr, KBr, CsBr, Bu 4 NCl, Bu 4 NBr, benzyltrimethylammonium bromide, trioctylmethylammonium bromide or tetraphenylphosphonium bromide are particularly preferred.
  • the cocatalyst is usually used in an amount of from 0.001 mol% to 100 mol%, in particular from 0.01 to 50 mol%, based on the compound of the formula (II). In the case of process engineering advantages, the reaction can also be carried out in the cocatalyst as a solvent (molten salt).
  • the reaction is generally carried out at a temperature between 20 and 200 ° C. preferably between 60 and 180 ° C, in particular between 80 and 160 ° C, and at a pressure up to 100 bar, preferably at a pressure between Normal pressure and 60 bar.
  • tumor values of the catalysts in of the order of 100,000 or more for bromoaromatics as starting materials as well as 10,000 and more can be realized for chloroaromatics. This Values correspond to the best known results with phosphine ligands were achieved.
  • the process according to the invention makes it possible for the first time to use extremely small amounts of catalyst, so that the catalyst costs in comparison to the known Suzuki reactions are not cost-limiting for the corresponding process.
  • catalyst contents of 1 to 2 mol%, usually ⁇ 1 mol%, particularly preferably ⁇ 0.2 mol%, are used in the process according to the invention.
  • phosphite ligands are easier and cheaper to produce, easier to modify and more stable to oxidation reactions.
  • the biaryls produced according to the invention are, among other things, technical used as intermediates for pharmaceuticals (ATII antagonists) and Agrochemicals, as ligand precursors for metallocene catalysts, optical brighteners and building blocks for polymers.
  • the solids are dissolved in 10 ml CH 2 Cl 2 and 10 ml 1N sodium hydroxide solution.
  • the organic phase is analyzed by gas chromatography.
  • the products are isolated by distillation, crystallization from methanol / acetone mixtures or by column chromatography (silica gel, hexane / ethyl acetate mixtures).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Steroid Compounds (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)

Claims (21)

  1. Procédé pour la préparation de biaryles mono-, bi- et/ou polyfonctionnels de formule générale Ar - Ar'   (I) dans laquelle Ar et Ar' représentent indépendamment l'un de l'autre
    un reste aromatique présentant jusqu'à 14 atomes de carbone,
    un composé hétéroaromatique pris dans le groupe des cycles à 5, 6 ou 7 chaínons comprenant au moins un atome d'azote, d'oxygène et/ou de soufre dans le cycle ;
    par réaction d'un halogénoaromatique de formule générale (II) Ar - X   (II) sur un composé de bore de formules générales (IIIa), (IIIb) et/ou (IIIc)
    Figure 00270001
    dans les formules (II), (IIIa), (IIIb) et (IIIc)
    Ar et Ar' possèdent les mêmes significations qu'à la formule (I) ;
    X est pris parmi les groupes chlore, brome, iode, OSO2CF3, OSO2-(aryle en C6-C10), OSO2-(alkyle en C1-C8) et N2 +Y-, Y représente un atome de chlore, de brome ou d'iode ou un anion tétrafluoroborate ou tétraphénylborate ;
    Q1 et Q2 indépendamment l'un de l'autre sont pris parmi les groupes OH, fluor, chlore, brome, iode, alkyle en C1-C4, aryle en C8-C10, alkoxy en C1-C4 et aryloxy en C8-C10 ;
    en présence d'au moins un complexe de palladium de formule générale (IVa) ou (IVb)
    Figure 00280001
    dans lesquels
    les restes R1 à R4 représentent indépendamment l'un de l'autre un reste alkyle en C1-C18 ou un reste Ar décrit auparavant ;
    E représente une liaison carbonée de 2 à 7 atomes de carbone ; et
    n et m indépendamment l'un de l'autre sont un nombre de 1 à 4,
    et on obtient les complexes de palladium de formule générale (IVa) ou (IVb) in situ à partir d'au moins un sel de palladium(II) ou d'un composé de palladium(0) et le ligand phosphite et le rapport molaire du composé de palladium (0) ou du sel de palladium(II) utilisé au ligand phosphite est compris entre 1:5 et 1:200.
  2. Procédé selon la revendication 1, caractérisé en ce que
    les restes aromatiques Ar et Ar' présentent jusqu'à huit substituants ;
    l'hétéroaromatique présente jusqu'à cinq substituants ; et/ou
    les restes R1 à R4 présentent jusqu'à huit substituants,
    qui sont pris indépendamment parmi les groupes comprenant fluor, chlore, CF3, OH, NO2, CN, R5, O-R5, CHO, CO-R5, COOH, COO-R5, OCO-R5, SiR3 5, NH2, NH-R5, N-R5 2, SO-R5, SO2-R5, SO3H, SO3R5, CONH2, NHCOH, NHCO-R5, NHCOO-R5, CHCH-CO2-(alkyle en C1-C8), PO-R5 2, P-R5 2, PO3H2, PO(alkyle en C1-C6)2 et CHCHCO2H ; R5 représente un reste alkyle présentant 1 à 8 atomes de carbone ou un reste aryle présentant 6 à 10 atomes de carbone, comme par exemple phényle.
  3. Procédé selon les revendications 1 ou 2, caractérisé en ce que la liaison carbonée E présente jusqu'à 7 substituants, qui sont pris indépendamment l'un de l'autre dans le groupe comprenant alkyle en C1-C4, O-alkyle en C1-C4, OH et Ar, Ar possédant la même signification qu'à la formule (I).
  4. Procédé selon les revendications 1 à 3, caractérisé en ce que à la formule (IIIa) Q1 et Q2 représentent indépendamment l'un de l'autre un reste alkyle en C1-C4, alkoxy en C1-C4, aryle en C6-C10 et/ou aryloxy en C6-C10, qui sont substitués par au moins un atome d'halogène ou un reste alkoxy en C1-C4 ou alkyle en C1-C4.
  5. Procédé selon les revendications 1 à 3, caractérisé en ce que, à la formule (IIIa), Q1 et Q2 représentent conjointement un groupe alkylènedioxy ou alkylène présentant jusqu'à quatre atomes de carbone, qui sont substitués par au moins un atome d'halogène ou un reste alkoxy en C1-C4 et/ou aryle en C6-C10.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que les restes Ar et Ar' représentent indépendamment l'un de l'autre un hétéroaromatique, le cycle hétéroaromatique étant condensé sur jusqu'à quatre autres cycles aromatiques, hétéroaromatiques et/ou aliphatiques.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que les restes Ar et Ar' indépendamment l'un de l'autre représentent un reste phényle, naphtyle, anthryle, phénanthryle, biphényle, pyridine, pyrimidine, oxazole, imidazole, pyrazine, quinoléine, indole, furanne, benzofuranne ou thiophène.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que les restes Ar et Ar' indépendamment l'un de l'autre présentent jusqu'à 5 substituants, pris parmi les groupes alkyle en C1-C8, O-(alkyle en C1-C8) OCO-(alkyle en C1-C8), N- (alkyle en C1-C8)2, phényle aryle, fluor, chlore, NO2, CN, COOH, CHO, SO2-(alkyle en C1-C4), NH- (alkyle en C1-C8), COO-(alkyle en C1-C8), CONH2, CONH-(alkyle en C1-C8), CO-(alkyle en C1-C6), CO-phényle et PO-phényle2.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que la réaction est mise en oeuvre en présence d'au moins un solvant pris dans le groupe comprenant l'eau, des éthers aliphatiques, des hydrocarbures aromatiques ou aliphatiques, des alcools, des esters, des nitriles aromatiques ou aliphatiques et des solvants aprotiques dipolaires comme des dialkylsulfoxydes, des N,N-dialkylamides d'acides carboxyliques aliphatiques ou des lactames alkylés.
  10. Procédé selon la revendication 9, caractérisé en ce que le solvant est THF, le dioxane, l'éther diéthylique, le diglyme, MTBE, DME, l'acétonitrile, le toluène, le xylène, l'anisole, l'acétate d'éthyle, le méthanol, l'éthanol, le butanol, l'éthylèneglycol, le carbonate d'éthylène, le carbonate de propylène, le diméthylsulfoxyde, le N,N-diméthylacétamide, le N,N-diméthylformamide ou la N-méthylpyrrolidone.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que la réaction est mise en oeuvre en présence d'au moins une base prise dans le groupe comprenant
    des amines primaires, secondaires et tertiaires, comme des alkylamines, des dialkylamines, des trialkylamines, qui peuvent être alicycliques ou à chaíne ouverte ;
    des sels de métaux alcalins et alcalino-terreux d'acides carboxyliques aliphatiques ou/et aromatiques, tels que des acétates, des propionates, des benzoates, en particulier des carbonates, des bicarbonates, des phosphates, des hydrogénophosphates ou/et hydroxydes ;
    des oxydes métalliques, en particulier des oxydes alcalins ou alcalino-terreux, comme le méthanolate de sodium, le méthanolate de potassium, le méthanolate de sodium, le méthanolate de magnésium et le méthanolate de calcium.
  12. Procédé selon la revendication 11, caractérisé en ce que la base est un carbonate, un hydroxyde ou phosphate de lithium, de sodium, de potassium, de calcium, de magnésium ou de césium.
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que la réaction est mise en oeuvre en présence d'au moins un sel fluorure, qui est notamment pris dans le groupe comprenant CaF2, NaF, KF, LiF, CsF et (alkyl en C1-C8)4NF.
  14. Procédé selon la revendication 1, caractérisé en ce que le composé de palladium(0) est pris dans le groupe des complexes de dibenzylidénacétone de palladium(0), de tétrakis(triphénylphosphite) de palladium(0), de tétrakis(triéthylphosphite) de palladium(0), de tétrakis(triphénylphosphane) de palladium(0), de bis(tri-o-tolylphosphane) de palladium(0), le complexe d'éther tricyclohexylphosphane-diallylique et le bis(tricyclo-hexylphosphane) de palladium(0).
  15. Procédé selon la revendication 1, caractérisé en ce que le sel de palladium(II) est pris dans le groupe comprenant l'acétate de palladium(II), le chlorure de palladium(II), le bromure de palladium(II), le tétrachloropalladate(II) de lithium, l'acétylacétonante de palladium(II), le propionate de palladium(II), le chlorure de bis(acétonitrile)-palladium(II), le dichlorure de bis(triphénylphosphane)-palladium(II) et le chlorure de bis(benzonitrile)-palladium(II).
  16. Procédé selon l'une des revendications précédentes, caractérisé en ce que la réaction est mise en oeuvre en présence d'au moins un co-catalyseur, pris dans le groupe de sels halogénures, en particulier un halogénure des éléments alcalins et/ou éléments alcalino-terreux, un halogénure d'ammonium ou/et un halogénure de phosphonium, de préférence un bromure ou/et chlorure.
  17. Procédé selon la revendication 16, caractérisé en ce que le sel halogénure est LiBr, LiCl, NaBr, KBr, CsBr, Bu4NCl, Bu4NBr, le bromure de benzyltriméthylammonium, le bromure de trioctylméthylammonium ou le bromure de tétraphénylphosphonium.
  18. Procédé selon les revendications 16 ou 17, caractérisé en ce qu'on utilise le co-catalyseur dans une quantité de 0,001 % molaire à 100 % molaires, en particulier de 0,01 à 50 % molaires, par rapport au composé de formule (II).
  19. Procédé selon l'une des revendications 16 à 18, caractérisé en ce que la réaction est mise en oeuvre en présence du co-catalyseur fondu (sel fondu).
  20. Procédé selon l'une des revendications précédentes, caractérisé en ce que la réaction est mise en oeuvre à une température comprise entre 20 et 200°C, de préférence entre 60 et 180°C, en particulier entre 80 et 160°C.
  21. Procédé selon l'une des revendications précédentes, caractérisé en ce que la réaction est mise en oeuvre sous une pression jusqu'à 100 bars, de préférence sous une pression comprise entre la pression normale et 60 bars.
EP00916828A 1999-04-10 2000-02-11 Procede de preparation de bi-aryles Expired - Lifetime EP1171406B1 (fr)

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DE19916222 1999-04-10
DE19916222A DE19916222A1 (de) 1999-04-10 1999-04-10 Verfahren zur Herstellung von Biarylen
PCT/EP2000/001111 WO2000061531A1 (fr) 1999-04-10 2000-02-11 Procede de preparation de bi-aryles

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EP (1) EP1171406B1 (fr)
JP (1) JP2002541232A (fr)
AT (1) ATE264828T1 (fr)
DE (2) DE19916222A1 (fr)
DK (1) DK1171406T3 (fr)
ES (1) ES2219325T3 (fr)
PT (1) PT1171406E (fr)
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EP2008991A1 (fr) 2007-06-29 2008-12-31 Bayer CropScience AG Procédé destiné à la fabrication de bi-aryles
JP2014129255A (ja) * 2012-12-28 2014-07-10 Fujifilm Corp 組成物およびフィルムならびにそれらの製造方法
CN113087591B (zh) * 2020-01-08 2022-05-03 浙江中欣氟材股份有限公司 一种2,2′,3,3′,5,5′,6,6′-八氟联苯的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3925437C1 (en) * 1988-12-17 1990-09-20 Bayer Ag, 5090 Leverkusen, De Bi:aryl cpds. prepn. - by coupling two halo-aromatic cpds.
DE59206518D1 (de) * 1991-02-25 1996-07-18 Hoffmann La Roche Flüssigkristalline Verbindungen mit endständigem 1-Alkinylrest
DE69233208T2 (de) 1991-11-18 2004-07-08 E.I. Du Pont De Nemours And Co., Wilmington Tetrazolylphenylborsäureintermediate zur synthese von aii rezeptor antagonisten
US5254776A (en) 1992-07-17 1993-10-19 Mallinckrodt Specialty Chemicals Company Synthesis of bromobiphenyls
DE4414499A1 (de) 1994-04-26 1995-11-02 Hoechst Ag Verfahren zur Kreuzkupplung von aromatischen Borverbindungen mit aromatischen Halogenverbindungen oder Perfluoralkylsulfonaten

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7425556B2 (en) 2005-12-20 2008-09-16 Astrazeneca Ab Compounds and uses thereof
US7465795B2 (en) 2005-12-20 2008-12-16 Astrazeneca Ab Compounds and uses thereof

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DE19916222A1 (de) 2000-10-19
EP1171406A1 (fr) 2002-01-16
US6566571B1 (en) 2003-05-20
WO2000061531A1 (fr) 2000-10-19
DE50006154D1 (de) 2004-05-27
PT1171406E (pt) 2004-08-31
ATE264828T1 (de) 2004-05-15
JP2002541232A (ja) 2002-12-03
DK1171406T3 (da) 2004-08-02
ES2219325T3 (es) 2004-12-01

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